Antireflective coating compositions comprising photoacid generators

ABSTRACT

The invention provides new light absorbing crosslinking compositions suitable for use as an antireflective composition, particularly for deep UV applications. The antireflective compositions of the invention comprise a photoacid generator that is activated during exposure of an overcoated photoresist. Antireflective compositions of the invention can significantly reduce undesired footing of an overcoated resist relief image.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions that reduce reflection ofexposing radiation from a substrate back into an overcoated photoresistlayer. More particularly, the invention relates to antireflectivecoating compositions that contain a photoacid generator compound thatcan reduce undesired footing or notching of an overcoated photoresistrelief image.

2. Background Art

Photoresists are photosensitive films used for transfer of an image to asubstrate. A coating layer of a photoresist is formed on a substrate andthe photoresist layer is then exposed through a photomask to a source ofactivating radiation. The photomask has areas that are opaque toactivating radiation and other areas that are transparent to activatingradiation. Exposure to activating radiation provides a photoinducedchemical transformation of the photoresist coating to thereby transferthe pattern of the photomask to the photoresist coated substrate.Following exposure, the photoresist is developed to provide a reliefimage that permits selective processing of a substrate.

A photoresist can be either positive-acting or negative-acting. For mostnegative-acting photoresists, those coating layer portions that areexposed to activating radiation polymerize or crosslink in a reactionbetween a photoactive compound and polymerizable reagents of thephotoresist composition. Consequently, the exposed coating portions arerendered less soluble in a developer solution than unexposed portions.For a positive-acting photoresist, exposed portions are rendered moresoluble in a developer solution while areas not exposed remaincomparatively less developer soluble. Photoresist compositions ingeneral are known to the art and described by Deforest, PhotoresistMaterials and Processes, McGraw Hill Book Company, New York, ch. 2, 1975and by Moreau, Semiconductor Lithography, Principles, Practices andMaterials, Plenum Press, New York, ch. 2 and 4, both incorporated hereinby reference for their teaching of photoresist compositions and methodsof making and using the same.

A major use of photoresists is in semiconductor manufacture where anobject is to convert a highly polished semiconductor slice, such assilicon or gallium arsenide, into a complex matrix of electronconducting paths, preferably of micron or submicron geometry, thatperform circuit functions. Proper photoresist processing is a key toattaining this object. While there is a strong interdependency among thevarious photoresist processing steps, exposure is believed to be one ofthe more important steps in attaining high resolution photoresistimages.

Reflection of activating radiation used to expose a photoresist oftenposes limits on resolution of the image patterned in the photoresistlayer. Reflection of radiation from the substrate/photoresist interfacecan produce spatial variations in the radiation intensity in thephotoresist, resulting in non-uniform photoresist linewidth upondevelopment. Radiation also can scatter from the substrate/photoresistinterface into regions of the photoresist where exposure is notintended, again resulting in linewidth variations. The amount ofscattering and reflection will typically vary from region to region,resulting in further linewidth non-uniformity.

Reflection of activating radiation also contributes to what is known inthe art as the "standing wave effect". To eliminate the effects ofchromatic aberration in exposure equipment lenses, monochromatic orquasi-monochromatic radiation is commonly used in photoresist projectiontechniques. Due to radiation reflection at the photoresist/substrateinterface, however, constructive and destructive interference isparticularly significant when monochromatic or quasi-monochromaticradiation is used for photoresist exposure. In such cases the reflectedlight interferes with the incident light to form standing waves withinthe photoresist. In the case of highly reflective substrate regions, theproblem is exacerbated since large amplitude standing waves create thinlayers of underexposed photoresist at the wave minima. The underexposedlayers can prevent complete photoresist development causing edge acuityproblems in the photoresist profile. The time required to expose thephotoresist is generally an increasing function of photoresist thicknessbecause of the increased total amount of radiation required to expose anincreased amount of photoresist. However, because of the standing waveeffect, the time of exposure also includes a harmonic component whichvaries between successive maximum and minimum values with thephotoresist thickness. If the photoresist thickness is non-uniform, theproblem becomes more severe, resulting in variable linewidths.

Variations in substrate topography also give rise to resolution-limitingreflection problems. Any image on a substrate can cause impingingradiation to scatter or reflect in various uncontrolled directions,affecting the uniformity of photoresist development. As substratetopography becomes more complex with efforts to design more complexcircuits, the effects of reflected radiation become more critical. Forexample, metal interconnects used on many microelectronic substrates areparticularly problematic due to their topography and regions of highreflectivity.

With recent trends towards high-density semiconductor devices, there isa movement in the industry to shorten the wavelength of exposure sourcesto deep ultraviolet (DUV) light (300 nm or less in wavelength), KrFexcimer laser light (248.4 nm) and ArF excimer laser light (193 nm). Theuse of shortened wavelengths of light for imaging a photoresist coatinghas generally resulted in increased reflection from the upper resistsurface as well as the surface of the underlying substrate. Thus, theuse of the shorter wavelengths has exacerbated the problems ofreflection from a substrate surface.

Another approach used to reduce the problem of reflected radiation hasbeen the use of a radiation absorbing layer interposed between thesubstrate surface and the photoresist coating layer. See, for example,PCT Application WO 90/03598, EPO Application No. 0 639 941 A1 and U.S.Pat. Nos. 4,910,122, 4,370,405 and 4,362,809, all incorporated herein byreference for their teaching of antireflective (antihalation)compositions and the use of the same. Such layers have also beenreferred to as antireflective layers or antireflective compositions or"ARCs".

In Shipley Company's European Application 542 008 A1 (incorporatedherein by reference) highly useful antihalation (antireflective)compositions are disclosed that comprise a resin binder and acrosslinker compound.

While it has been found that prior antireflective compositions may beeffective for many antireflective applications, prior compositions alsomay pose some potential performance limitations, e.g. when theantireflective compositions are used with resist compositions to patternfeatures of sub-micron or sub-half micron dimensions. In particular, useof at least some prior antireflective compositions has resulted inundercutting of a developed resist relief image, known in the art as"notching". Another problem has been "footing", i.e. the failure toclear during development that results in an upwardly tapering reliefimage sidewall. Both notching and footing can compromise the resolutionof the image patterned onto the underlying substrate.

It thus would be desirable to have new antireflective coatingcompositions.

SUMMARY OF THE INVENTION

The present invention provides new light absorbing compositions suitablefor use as antireflective coating compositions, particularly for deep UVapplications. The antireflective compositions of the invention ingeneral comprise a resin binder and a photoacid generator that canreduce undesired notching and footing of an overcoated photoresistrelief image.

It is believed that acids produced by photoacid generators ofphotoresists, particularly the strong photogenerated acids ofchemically-amplified resists, can be highly susceptible to acidneutralization, particularly via base contamination from a substrate orantireflective composition coating layer that underlies a resist layer.Photogenerated acid loss from a resist layer also can occur viadiffusion of the acid into an underlying antireflective compositioncoating layer. In either case of neutralization or diffusion, acid losscan compromise the resolution of the developed resist layer. Typicaleffects are footing or notching at the base of a resist relief imagewhere the photogenerated acid concentration has been most significantlyreduced through such diffusion or neutralization processes.

By incorporating a photoacid generator into the underlyingantireflective composition coating layer in accordance with the presentinvention, sufficient acid can be generated in the antireflectivecomposition layer during exposure of the resist layer to avoid such acidloss from the resist layer and to ensure that an effective amount ofacid is present throughout the thickness of the resist layer. In otherwords, acid diffusion or neutralization from a resist layer can becompensated for by the presence of photogenerated acid in theantireflective composition layer and at the antireflectivecomposition/resist layers interface. As a result, resist relief imageshaving vertical profiles with little or no footing or notching can beproduced. See, for instance, the results of the examples and comparativeexamples which follow.

In the case of crosslinking antireflective compositions of theinvention, preferably the antireflective composition photoacid generatoris not substantially activated during crosslinking of the antireflectivecomposition. In particular, with respect to antireflective compositionsthat are thermally crosslinked, the antireflective composition PAGshould be substantially stable to the conditions of the crosslinkingreaction so that the PAG can be activated and generate acid duringsubsequent exposure of an overcoated resist layer. Specifically,preferred PAGs do not substantially decompose or otherwise degrade uponexposure of temperatures of from about 140 or 150 to 190° C. for 5 to 30or more minutes.

For at least some antireflective compositions of the invention,antireflective composition photoacid generators will be preferred thatcan act as surfactants and congregate near the upper portion of theantireflective composition layer proximate to the antireflectivecomposition/resist coating layers interface. Thus, for example, suchpreferred PAGs may include extended aliphatic groups, e.g. substitutedor unsubstituted alkyl or alicyclic groups having 4 or more carbons,preferably 6 to 15 or more carbons, or fluorinated groups such as C₁₋₁₅alkyl or C₂₋₁₅ alkenyl having one or preferably two or more fluorosubstituents.

Particularly preferred antireflective composition photoacid generatorsof the invention can be activated upon exposure to deep UV radiation,particularly about 248 nm and/or about 193 nm, so that theantireflective composition can be effectively used with overcoated deepUV photoresists. Suitably the photoacid generator of the antireflectivecomposition and the photoacid generator of the photoresist compositionwill be activated at the same exposure wavelength. Sensitizer materialsformulated into the photoresist composition and/or antireflectivecompositions also can be used to ensure that a single exposurewavelength will activate the photoacid generators of both theantireflective and photoresist compositions.

It is further preferred that an antireflective composition of theinvention is used together with a photoresist composition where theantireflective composition photoactive compound and photoresistphotoactive compound generate the same or approximately the same acidcompound (photoproduct) upon exposure to activating radiation duringirradiation of the photoresist layer, i.e. photoproducts that preferablyhave similar diffusion characteristics and similar acid strengths. Ithas been found that resolution of an overcoated resist relief image iseven further enhanced with such matching of the respectiveantireflective composition and resist photoacid products. Referencesherein to "substantially the same" antireflective composition and resistphotoacid products means that those two photoproducts differ no morethan no about 2 or 2.5 in pK_(a) values (measured at 25° C.), preferablythe two photoproducts differ no more than about 1 or 1.5 in pK_(a)values, and still further preferably the two photoproducts differ nomore than about 0.75 in pK_(a) values. It is further preferred that such"substantially the same" antireflective composition and resist photoacidproducts differ in molecular weight by no more than about 40 percent,preferably by no more than about 20 percent, still more preferably by nomore than about 15 percent. It is still further preferred that theantireflective composition and resist photoproducts are each of the sameclass of acids, e.g. that both photoproducts are sulfonate acids or bothare halo-acids such as HBr and the like.

Preferred antireflective compositions of the invention contain a resinbinder that contain one or more moieties that are chromophores for theexposure radiation of an overcoated resist composition, i.e. themoieties are capable of absorbing exposure radiation to thereby reducereflections. For example, for preferred antireflective compositions usedwith a deep UV (DUV) photoresist, preferred chromophores includeanthracenyl, particularly alkylene anthracene esters such as pendantgroups of the formula --(C.tbd.O)O(CH₂)_(n) anthracene, wherein n is aninteger from 1 to about 6. Other preferred chromophores includequinolinyl and ring-substituted quinolinyl derivatives such ashydroxyquinolinyl, phenanthrenyl and acridine groups. Suitably about 5to 90 percent of the units of a resin comprise such a chromophore, morepreferably about 10 to 60 percent. Preferred resin binders of theinvention have an optical density of at least about 4 units/μ at theexposure wavelength (e.g. 193 nm or 248 nm). Preferred resin bindersalso are capable of reaction with the crosslinker component, e.g. by ahydroxy or carboxy moiety on the resin or a "masked" moiety such as anester that can generate such a reactive group in the presence of acid orotherwise. Preferred antireflective composition resin binders withchromophore moieties are copolymers and are prepared by polymerizing twoor more different monomers where at least one of the monomers includes achromophore group. It has been found that this synthesis providesdistinct advantages over functionalization of a preformed polymer to addchromophore groups.

Crosslinking antireflective compositions of the invention preferablyalso contain an acid or thermal acid generator to induce or promotecrosslinking of one or more components of the antireflectivecomposition. Generally preferred crosslinking antireflectivecompositions comprise a separate crosslinker component such as anamine-based material, e.g. a glycouril, benzoguanamine or melamineresin. Glycouril resins are particularly preferred, especiallyPowderlink 1174 available from American Cyanamid.

Antireflective compositions of the invention are most preferably used incombination with positive-acting chemically amplified photoresistcompositions. Antireflective compositions of the invention are alsosuitably used with negative-acting photoresists as well as other typesof positive resists.

The invention further provides methods for forming a photoresist reliefimage and novel articles of manufacture comprising substrates coatedwith an antireflective composition of the invention alone or incombination with a photoresist composition. Other aspects of theinvention are disclosed infra.

DETAILED DESCRIPTION OF THE INVENTION

Antireflective compositions of the invention comprise one or morephotoacid generators (i.e. "PAG") that are suitably employed in anamount sufficient to inhibit or substantially prevent undesired notchingor footing of an overcoated photoresist layer. Suitable amounts of thePAG can vary rather widely and can be readily determined empirically. Ingeneral, the one or more PAGs of an antireflective composition of theinvention may be suitably employed in amounts of about 0.25 to 5 weightpercent or less based on total weight of the antireflective composition.See the examples which follow for exemplary amounts. Particularlypreferred amounts of a PAG of an antireflective composition also mayvary depending on the characteristics and processing conditions of thephotoresist that is used with the antireflective composition. Forinstance, if the photoresist photoacid generator produces a relativelystrong acid photoproduct whereby the photoresist is post-exposure baked(PEB) at relatively low temperatures, then the photoacid product of theantireflective composition will be less likely to thermally decompose atsuch low PEB temperatures, resulting in a relatively higher effectiveconcentration of acid in the antireflective composition. Accordingly,that antireflective composition can be effectively formulated with arelatively lower concentration of photoacid generator. Conversely, if aphotoresist is used that is post-exposure baked at relatively hightemperatures, then a portion of the photoacid product of theantireflective composition may be more likely to be thermallydecomposed. In such case, the antireflective composition may beformulated with a relatively higher concentration of photoacid generatorto ensure an effective concentration of photogenerated acid and maximumreductions of undesired footing.

Sulfonate compounds are preferred PAGs for antireflective compositionsof the invention, particularly sulfonate salts. Two specificallypreferred agents are the following PAGS 1 and 2: ##STR1##

Such sulfonate compounds can be prepared as disclosed in Example 2 whichfollows, which details the synthesis of above PAG 1. Sulfonate PAG 2above can be prepared by the same procedures of Example 2 which follows,except approximately molar equivalents of t-butyl benzene and benzenewould be reacted together in the first step with acetic anhydride andKIO₃.

Other suitable sulfonate PAGS including sulfonated esters andsulfonyloxy ketones. See J. of Photopolymer Science and Technology,4(3):337-340 (1991), for disclosure of suitable sulfonate PAGS,including benzoin tosylate, t-butylphenylalpha-(p-toluenesulfonyloxy)-acetate and t-butylalpha-(p-toluenesulfonyloxy)-acetate. Preferred sulfonate PAGs are alsodisclosed in U.S. Pat. No. 5,344,742 to Sinta et al.

Onium salts also may be employed as photoacid generators ofantireflective compositions of the invention. Onium salts that areweakly nucleophilic anions have been found to be particularly suitable.Examples of such anions are the halogen complex anions of divalent toheptavalent metals or non-metals, for example, Sb, Sn, Fe, Bi, Al, Ga,In, Ti, Zr, Sc, D, Cr, Hf, and Cu as well as B, P, and As. Examples ofsuitable onium salts are diaryl-diazonium salts and onium salts of groupVa and B, Ia and B and I of the Periodic Table, for example, haloniumsalts, quaternary ammonium, phosphonium and arsonium salts, aromaticsulfonium salts and sulfoxonium salts or selenium salts. Examples ofsuitable preferred onium salts can be found in U.S. Pat. Nos. 4,442,197;4,603,101; and 4,624,912.

Other useful acid generators for antireflective compositions of theinvention include the family of nitrobenzyl esters, and the s-triazinederivatives. Suitable s-triazine acid generators are disclosed, forexample, in U.S. Pat. No. 4,189,323.

Halogenated non-ionic, photoacid generating compounds also may besuitable for antireflective compositions of the invention such as, forexample, 1,1-bis p-chlorophenyl!-2,2,2-trichloroethane (DDT); 1,1-bisp-methoxyphenyl!-2,2,2-trichloroethane;1,2,5,6,9,10-hexabromocyclodecane; 1,10-dibromodecane; 1,1-bisp-chlorophenyl!-2,2-dichloroethane; 4,4-dichloro-2-(trichloromethyl)benzhydrol (Kelthane); hexachlorodimethyl sulfone;2-chloro-6-(trichloromethyl) pyridine;o,o-diethyl-o-(3,5,6-trichloro-2-pyridyl)phosphorothionate;1,2,3,4,5,6-hexachlorocyclohexane; N(1,1-bisp-chlorophenyl!-2,2,2-trichloroethyl)acetamide; tris2,3-dibromopropyl!isocyanurate; 2,2-bisp-chlorophenyl!-1,1-dichloroethylene; tris trichloromethyl!s-triazine;and their isomers, analogs, homologs, and residual compounds. Suitablephotoacid generators are also disclosed in European Patent ApplicationNos. 0164248 and 0232972. Acid generators preferred for deep U.V.exposure include 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (DDT);1,1-bis(p-methoxyphenol)-2,2,2-trichloroethane;1,1-bis(chlorophenyl)-2,2,2 trichloroethanol;tris(1,2,3-methanesulfonyl)benzene; and tris(trichloromethyl)triazine.

As discussed above, the resin binder component of the antireflectivecompositions of the invention preferably will effectively absorbreflections in the deep UV range (typically from about 100 to 300 nm).Thus, the resin binder preferably contains units that are deep UVchromophores, i.e. units that absorb deep UV radiation. Highlyconjugated moieties are generally suitable chromophores. Aromaticgroups, particularly polycyclic hydrocarbon or heterocyclic units, aretypically preferred deep UV chromophores, e.g. groups having from two tothree or four fused or separate rings with 3 to 8 ring members in eachring and zero to three N, O or S atoms per ring. Such chromophoresinclude substituted and unsubstituted phenanthryl, substituted andunsubstituted anthracyl, substituted and unsubstituted acridine,substituted and unsubstituted naphthyl, substituted and unsubstitutedquinolinyl and ring-substituted quinolinyls such as hydroxyquinolinylgroups. Substituted or unsubstituted anthracyl groups are particularlypreferred. For example, preferred resin binders have pendant anthracylgroups, particularly acrylic resins of the following Formula (I):##STR2##

wherein each R and R¹ is independently a hydrogen or a substituted orunsubstituted alkyl group having from 1 to about 8 carbon atoms,preferably substituted or unsubstituted C₁₋₆ alkyl;

each R² is independently substituted or unsubstituted alkyl having 1 toabout 10 carbon atoms, more typically 1 to about 6 carbons;

each R³ may be independently halogen (particularly F, Cl and Br), alkylhaving 1 to about 8 carbon atoms, alkoxy having 1 to about 8 carbonatoms, alkenyl having 2 to about 8 carbon atoms, alkynyl having 2 toabout 8 carbon atoms, cyano, nitro, etc.;

m is an integer of from 0 (where the anthracyl ring is fullyhydrogen-substituted) to 9, and preferably m is 0, 1 or 2;

x is the mole fraction or percent of alkyl acrylate units in the polymerand preferably is from about 10 to about 80 percent; and y is the molefraction or percent of anthracene units in the polymer and preferably isfrom about 5 to 10 to 90 percent. The polymer also may contain otherunits if desired, but preferably the polymer will contain at least about10 mole percent of anthracene units. Hydroxyalkyl is a particularlypreferred R² group, especially alkyl having a primary hydroxy group suchas where R² is 2-hydroxyethylene (--CH₂ CH₂ OH). Preferably the resinbinder contains 9-(methylene)anthracene ester units.

Another preferred resin binder comprises substituted or unsubstitutedquinolinyl or a quinolinyl derivative that has one or more N, O or Sring atoms such as a hydroxyquinolinyl. The polymer may contain otherunits such as carboxy and/or alkyl ester units pendant from the polymerbackbone. A particularly preferred antireflective composition resinbinder is an acrylic polymer of the following Formula (II): ##STR3##

wherein each R⁴ and R⁵ is independently a hydrogen or a substituted orunsubstituted alkyl group having from 1 to about 8 carbon atoms,preferably substituted or unsubstituted C₁₋₆ alkyl;

each R⁶ is independently substituted or unsubstituted alkyl having 1 toabout 10 carbon atoms, more typically 1 to about 6 carbons;

W is a bond or substituted or unsubstituted alkylene having 1 to about 4carbons, and preferably is a bond;

Z is a carbon, nitrogen, oxygen or sulfur;

each R⁷ may be independently halogen (particularly F, Cl and Br), alkylhaving 1 to about 8 carbon atoms, alkoxy having 1 to about 8 carbonatoms, alkenyl having 2 to about 8 carbon atoms, alkynyl having 2 toabout 8 carbon atoms, cyano, nitro, etc.;

n is an integer of from 0 (where the ring is fully hydrogen-substituted)to 7, and preferably n is 0, 1 or 2.

x' is the mole fraction or percent of alkyl acrylate units in thepolymer and preferably is from 10 to about 80 percent; and y' is themole fraction or percent of quinolinyl or hydroxyquinolinyl units in thepolymer and preferably is from about 5 to about 90 percent. The polymeralso may contain other units if desired, but preferably the polymer willcontain at least about 10 mole percent of quinolinyl and/orhydroxyquinolinyl units. Hydroxyalkyl is a particularly preferred R⁶group, especially alkyl having a primary hydroxy group such as where R⁶is 2-hydroxyethylene.

The above-mentioned substituted groups (including substituted groups R¹through R⁷ and W and substituted PAG substituents) may be substituted atone or more available positions by one or more suitable groups such ase.g. halogen (particularly F, Cl and Br); cyano; hydroxyl, nitro,alkanoyl such as a C₁₋₆ alkanoyl group such as acyl and the like; alkylgroups having from 1 to about 8 carbon atoms; alkenyl and alkynyl groupshaving one or more unsaturated linkages and 2 to about 8 carbon atoms;alkoxy groups having from 1 to about 6 carbons; etc.

Resin binders for antireflective compositions of the invention arepreferably synthesized by polymerizing two or more different monomerswhere at least one of the monomers includes a chromophore group, e.g. ananthracenyl, quinolinyl or hydroxyquinolinyl group. A free radicalpolymerization is suitably employed, e.g., by reaction of a plurality ofmonomers to provide the various units in the presence of a radicalinitiator preferably under an inert atmosphere (e.g., N₂ or argon) andat elevated temperatures such as about 70° C. or greater, althoughreaction temperatures may vary depending on the reactivity of theparticular reagents employed and the boiling point of the reactionsolvent (if a solvent is employed). See Example 1 which follows forexemplary reaction conditions. Suitable reaction temperatures for anyparticular system can be readily determined empirically by those skilledin the art based on the present disclosure. A reaction solvent may beemployed if desired. Suitable solvents include alcohols such aspropanols and butanols and aromatic solvents such as benzene,chlorobenzene, toluene and xylene. Dimethylsulfoxide, dimethylformamideand THF are also suitable. The polymerization reaction also may be runneat. A variety of free radical initiators may be employed to preparethe copolymers of the invention. For example, azo compounds may beemployed such as azo-bis-2,2'-isobutyronitrile (AIBN) and 1,1'-azobis(cyclohexanecarbonitrile). Peroxides, peresters, peracids andpersulfates also can be employed.

Also, while less preferred, a preformed resin may be functionalized withchromophore units. For example, a glycidyl phenolic resin such as aglycidyl novolac can be reacted with an anthranyl carboxylic acid.

Resin binders of antireflective compositions of the invention preferablyexhibit good absorbance at deep UV wavelengths such as within the rangeof from 100 to about 300 nm. More specifically, preferred resin bindersof the invention have optical densities of at least about 3 absorbanceunits per micron (Absorb. units/μ) at the exposing wavelength utilized(e.g. about 248 nm or about 193 nm), preferably from about 5 to 20 ormore absorbance units per micron at the exposing wavelength, morepreferably from about 4 to 16 or more absorbance units per micron at theexposing wavelength utilized. Higher absorbance values for a particularresin can be obtained by increasing the percentage of chromophore unitson the resin.

Preferably resin binders of the above formulae will have a weightaverage molecular weight (Mw) of about 1,000 to about 10,000,000daltons, more typically about 5,000 to about 1,000,000 daltons, and amolecular number molecular weight (Mn) of about 500 to about 1,000,000daltons. Molecular weights (either Mw or Mn) of the polymers of theinvention are suitably determined by gel permeation chromatography.

While antireflective composition resin binders having such absorbingchromophores are generally preferred, antireflective compositions of theinvention may comprise other resins either as a co-resin or as the soleresin binder component. For example, phenolics, e.g. poly(vinylphenols)and novolaks, may be employed. Such resins are disclosed in theincorporated European Application EP 542008 of the Shipley Company.Other resins described below as photoresist resin binders also could beemployed in resin binder components of antireflective compositions ofthe invention.

The concentration of the resin binder component of the antireflectivecompositions of the invention may vary within relatively broad ranges,and in general the resin binder is employed in a concentration of fromabout 50 to 95 weight percent of the total of the dry components of theantireflective composition, more typically from about 60 to 90 weightpercent of the total dry components (all components except solventcarrier).

Crosslinking-type antireflective compositions of the invention alsocontain a crosslinker component. A variety of crosslinkers may beemployed, including those antireflective composition crosslinkersdisclosed in Shipley European Application 542008 incorporated herein byreference. For example, suitable antireflective composition crosslinkersinclude amine-based crosslinkers such as a melamine materials, includingmelamine resins such as manufactured by American Cyanamid and sold underthe tradename of Cymel 300, 301, 303, 350, 370, 380, 1116 and 1130.Glycourils are particularly preferred including glycourils availablefrom American Cyanamid. Benzoquanamines and urea-based materials alsowill be suitable including resins such as the benzoquanamine resinsavailable from American Cyanamid under the name Cymel 1123 and 1125, andurea resins available from American Cyanamid under the names of Beetle60, 65 and 80. In addition to being commercially available, suchamine-based resins may be prepared e.g. by the reaction of acrylamide ormethacrylamide copolymers with formaldehyde in an alcohol-containingsolution, or alternatively by the copolymerization of N-alkoxymethylacrylamide or methacrylamide with other suitable monomers.

Low basicity antireflective composition crosslinkers are particularlypreferred such as a methoxy methylated glycouril. A specificallypreferred crosslinker is a methoxy methylated glycouril corresponding tothe following structure (III): ##STR4##

This methoxy methylated glycouril can be prepared by known procedures.The compound is also commercially available under the tradename ofPowderlink 1174 from the American Cyanamid Co.

Other suitable low basicity crosslinkers include hydroxy compounds,particularly polyfunctional compounds such as phenyl or other aromaticshaving one or more hydroxy or hydroxy alkyl substituents such as a C₁₋₈hydroxyalkyl substituents. Phenol compounds are generally preferred suchas di-methanolphenol (C₆ H₃ (CH₂ OH)₂ OH) and other compounds havingadjacent (within 1-2 ring atoms) hydroxy and hydroxyalkyl substitution,particularly phenyl or other aromatic compounds having one or moremethanol or other hydroxylalkyl ring substituent and at least onehydroxy adjacent such hydroxyalkyl substituent.

It has been found that a low basicity crosslinker such as a methoxymethylated glycouril used in antireflective compositions of theinvention can provide excellent lithographic performance properties,including significant reduction (SEM examination) of undercutting orfooting of an overcoated photoresist relief image.

A crosslinker component of antireflective compositions of the inventionin general is present in an amount of between 5 and 50 weight percent oftotal solids (all components except solvent carrier) of theantireflective composition, more typically in an amount of about 7 to 25weight percent total solids.

Crosslinking antireflective compositions of the invention preferablyfurther comprise an acid or thermal acid generator compound forcatalyzing or promoting crosslinking during curing of an antireflectivecomposition coating layer. Preferably a thermal acid generator isemployed, i.e. a compound that generates acid upon thermal treatment. Avariety of known thermal acid generators are suitably employed such ase.g. 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyltosylate and other alkyl esters of organic sulfonic acids. Compoundsthat generate a sulfonic acid upon activation are generally suitable.Typically a thermal acid generator is present in an antireflectivecomposition in concentration of from about 0.1 to 10 percent by weightof the total of the dry components of the composition, more preferablyabout 2 percent by weight of the total dry components.

Also, as discussed above, rather than a thermal acid generator, an acidmay be simply formulated into the antireflective composition,particularly for antireflective compositions that require heating tocure in the presence of acid so that the acid does not promote undesiredreaction of composition components prior to use of the antireflectivecomposition. Suitable acids include e.g. strong acids such as sulfonicacids such as toluene sulfonic acid and sulfonic acid, triflic acid, ormixtures of those materials.

The present invention also includes antireflective compositions that donot undergo significant cross-linking during intended use with aphotoresist composition. Such non-crosslinking antireflectivecompositions include a photoacid generator as disclosed herein, but neednot include a crosslinker component or an acid or thermal acid generatorfor inducing or promoting a crosslinking reaction. In other words, suchnon-crosslinking antireflective compositions typically will beessentially free (i.e. less than about 1 or 2 weight percent) orcompletely free of a crosslinker component and/or a thermal acidgenerator.

Antireflective compositions of the invention also may contain additionaldye compounds that absorb radiation used to expose an overcoatedphotoresist layer. Other optional additives include surface levelingagents, for example, the leveling agent available under the tradenameSilwet 7604 from Union Carbide, or the surfactant FC 171 or FC 431available from the 3M Company.

To make a liquid coating composition, the components of theantireflective composition are dissolved in a suitable solvent such as,for example, ethyl lactate or one or more of the glycol ethers such as2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, andpropylene glycol monomethyl ether; solvents that have both ether andhydroxy moieties such as methoxy butanol, ethoxy butanol, methoxypropanol and ethoxy propanol; esters such as methyl cellosolve acetate,ethyl cellosolve acetate, propylene glycol monomethyl ether acetate,dipropylene glycol monomethyl ether acetate and other solvents such asdibasic esters, propylene carbonate and gamma-butyro lactone. Theconcentration of the dry components in the solvent will depend onseveral factors such as the method of application. In general, thesolids content of an antireflective composition varies from about 0.5 to20 weight percent of the total weight of the antireflective composition,preferably the solids content varies from about 2 to 10 weight percentof the total weight of the antireflective composition.

A variety of photoresist compositions can be employed with theantireflective compositions of the invention, including positive-actingand negative-acting photoacid-generating compositions. Photoresists usedwith antireflective compositions of the invention typically comprise aresin binder and a photoactive component, typically a photoacidgenerator compound. Preferably the photoresist resin binder hasfunctional groups that impart alkaline aqueous developability to theimaged resist composition.

As discussed above, particularly preferred photoresists for use withantireflective compositions of the invention are chemically-amplifiedresists, particularly positive-acting chemically-amplified resistscompositions, where the photoactivated acid in the resist layer inducesa deprotection-type reaction of one or more composition components tothereby provide solubility differentials between exposed and unexposedregions of the resist coating layer.

A number of chemically-amplified resist compositions have beendescribed, e.g., in U.S. Pat. Nos. 4,968,581; 4,883,740; 4,810,613;4,491,628 and 5,492,793, all of which are incorporated herein byreference for their teaching of making and using chemically amplifiedpositive-acting resists. A particularly preferred chemically amplifiedphotoresist for use with an antireflective composition of the inventioncomprises in admixture a photoacid generator and a resin binder thatcomprises a copolymer containing both phenolic and non-phenolic units.For example, one preferred group of such copolymers has acid labilegroups substantially, essentially or completely only on non-phenolicunits of the copolymer. One especially preferred copolymer binder hasrepeating units x and y of the following formula: ##STR5##

wherein the hydroxyl group be present at either the ortho, meta or parapositions throughout the copolymer, and R' is substituted orunsubstituted alkyl having 1 to about 18 carbon atoms, more typically 1to about 6 to 8 carbon atoms. Tert-butyl is a generally preferred R'group. An R' group may be optionally substituted by e.g. one or morehalogen (particularly F, Cl or Br), C₁₋₈ alkoxy, C₂₋₈ alkenyl, etc. Theunits x and y may be regularly alternating in the copolymer, or may berandomly interspersed through the polymer. Such copolymers can bereadily formed. For example, for resins of the above formula, vinylphenols and a substituted or unsubstituted alkyl acrylate such ast-butylacrylate and the like may be condensed under free radicalconditions as known in the art. The substituted ester moiety, i.e.R'--O--C(═O)--, moiety of the acrylate units serves as the acid labilegroups of the resin and will undergo photoacid induced cleavage uponexposure of a coating layer of a photoresist containing the resin.Preferably the copolymer will have a Mw of from about 8,000 to about50,000, more preferably about 15,000 to about 30,000 with a molecularweight distribution of about 3 or less, more preferably a molecularweight distribution of about 2 or less. Non-phenolic resins, e.g. acopolymer of an alkyl acrylate such as t-butylacrylate ort-butylmethacrylate and a vinyl alicyclic such as a vinyl norbornyl orvinyl cyclohexanol compound, also may be used as a resin binder incompositions of the invention. Such copolymers also may be prepared bysuch free radical polymerization or other known procedures and suitablywill have a Mw of from about 8,000 to about 50,000, and a molecularweight distribution of about 3 or less. Additional preferredchemically-amplified positive resists are disclosed in U.S. Pat. No.5,258,257 to Sinta et al.

The antireflective compositions of the invention also may be used withother positive resists, including those that contain resin binders thatcomprise polar functional groups such as hydroxyl or carboxylate and theresin binder is used in a resist composition in an amount sufficient torender the resist developable with an aqueous alkaline solution.Generally preferred resist resin binders are phenolic resins includingphenol aldehyde condensates known in the art as novolak resins, homo andcopolymers or alkenyl phenols and homo and copolymers ofN-hydroxyphenyl-maleimides.

Copolymers containing phenol and nonaromatic cyclic alcohol units alsoare preferred resin binders for resists of the invention and may besuitably prepared by partial hydrogenation of a novolak orpoly(vinylphenol) resin. Such copolymers and the use thereof inphotoresist compositions are disclosed in U.S. Pat. No. 5,128,232 toThackeray et al.

Preferred negative-acting resist compositions for use with anantireflective composition of the invention comprise a mixture ofmaterials that will cure, crosslink or harden upon exposure to acid, anda photoacid generator.

Particularly preferred negative-acting resist compositions comprise aresin binder such as a phenolic resin, a crosslinker component and aphotoactive component of the invention. Such compositions and the usethereof have been disclosed in European Patent Applications 0164248 and0232972 and in U.S. Pat. No. 5,128,232 to Thackeray et al. Preferredphenolic resins for use as the resin binder component include novolaksand poly(vinylphenol)s such as those discussed above. Preferredcrosslinkers include amine-based materials, including melamine,glycourils, benzoguanamine-based materials and urea-based materials.Melamine-formaldehyde resins are generally most preferred. Suchcrosslinkers are commercially available, e.g. the melamine resins soldby American Cyanamid under the trade names Cymel 300, 301 and 303.Glycouril resins are sold by American Cyanamid under trade names Cymel1170, 1171, 1172, Powderlink 1174, urea-based resins are sold under thetrade names of Beetle 60, 65 and 80, and benzoguanamine resins are soldunder the trade names Cymel 1123 and 1125.

Suitable photoacid generator compounds of resists used withantireflective compositions of the invention include the onium salts,such as those disclosed in U.S. Pat. Nos. 4,442,197, 4,603,101, and4,624,912, each incorporated herein by reference; and non-ionic organicphotoactive compounds such as the halogenated photoactive compounds asin U.S. Pat. No. 5,128,232 to Thackeray et al. and sulfonate photoacidgenerators including sulfonated esters and sulfonyloxy ketones. See J.of Photopolymer Science and Technology, 4(3):337-340 (1991), fordisclosure of suitable sulfonate PAGS, including benzoin tosylate,t-butylphenyl alpha-(p-toluenesulfonyloxy)-acetate and t-butylalpha-(p-toluenesulfonyloxy)-acetate. Preferred sulfonate PAGs are alsodisclosed in U.S. Pat. No. 5,344,742 to Sinta et al. The abovecamphorsulfonate PAGs 1 and 2 are also preferred photoacid generatorsfor resist compositions used with the antireflective compositions of theinvention, particularly chemically-amplified resists of the invention.

Photoresists for use with an antireflective composition of the inventionalso may contain other materials. For example, other optional additivesinclude actinic and contrast dyes, anti-striation agents, plasticizers,speed enhancers, etc. Such optional additives typically will be presentin minor concentration in a photoresist composition except for fillersand dyes which may be present in relatively large concentrations suchas, e.g., in amounts of from 5 to 30 percent by weight of the totalweight of a resist's dry components.

Antireflective compositions of the invention that include a low basicitycrosslinker such as a suitable glycouril are particularly useful withphotoresists that generate a strong acid photoproduct upon exposure suchas triflic acid, camphor sulfonate or other sulfonic acid, or other acidhaving a pKa (25° C.) of about 2 or less. Without wishing to be bound bytheory, it is believed that antireflective compositions of the inventionare particularly effective with such strong acid resists because thestrong photogenerated acid will migrate from the resist and remain inthe antireflective composition layer to a lesser extent relative to acomparable antireflective composition that contains a more basiccrosslinker. That is, the low basicity crosslinkers of the inventionwill tie up strong photogenerated acids of an overcoated resist layer toa lesser extent than a more basic antireflective compositioncrosslinker. As a result, less acid loss from the resist layer willoccur and resolution problems such as footing will be even furtherreduced.

In use, an antireflective composition of the invention is applied as acoating layer to a substrate may any of a variety of methods such asspin coating. The antireflective composition in general is applied on asubstrate with a dried layer thickness of between about 0.02 and 0.5 μm,preferably a dried layer thickness of between about 0.04 and 0.20 μm.The substrate is suitably any substrate used in processes involvingphotoresists. For example, the substrate can be silicon, silicon dioxideor aluminum-aluminum oxide microelectronic wafers. Gallium arsenide,ceramic, quartz or copper substrates may also be employed. Substratesused for liquid crystal display or other flat panel display applicationsare also suitably employed, for example glass substrates, indium tinoxide coated substrates and the like. Substrates for optical andoptical-electronic devices (e.g. waveguides) also can employed.

Preferably the antireflective layer is cured before a photoresistcomposition is applied over the antireflective composition. Cureconditions will vary with the components of the antireflectivecomposition. Thus, if the composition does not contain an acid orthermal acid generator, cure temperatures and conditions will be morevigorous than those of a composition containing an acid or acidgenerator compound. Typical cure conditions are from about 120° C. to225° C. for about 0.5 to 40 minutes. Cure conditions preferably renderthe antireflective composition coating layer substantially insoluble tothe photoresist solvent as well as an alkaline aqueous developersolution.

After such curing a photoresist is applied over the surface of theantireflective composition. As with application of the antireflectivecomposition, the photoresist can be applied by any standard means suchas by spinning, dipping, meniscus or roller coating. Followingapplication, the photoresist coating layer is typically dried by heatingto remove solvent preferably until the resist layer is tack free.Optimally, essentially no intermixing of the antireflective compositionlayer and photoresist layer should occur.

The resist layer is then imaged with activating radiation through a maskin conventional manner. The exposure energy is sufficient to effectivelyactivate the photoactive component of the resist system to produce apatterned image in the resist coating layer as well as activate thephotoacid generator of at least a portion of the thickness ofantireflective composition layer so that photogenerated acid from thePAG of the antireflective composition is present at the antireflectivecomposition/resist coating layers interface. Typically, the exposureenergy typically ranges from about 3 to 300 mJ/cm² and depending in partupon the exposure tool and the particular resist and resist processingthat is employed. Generally, exposure doses used for typical imaging ofa resist layer will be sufficient to photoactivate an effective of acidin the underlying antireflective composition layer.

The exposed resist layer may be subjected to a post-exposure bake ifdesired to create or enhance solubility differences between exposed andunexposed regions of a coating layer. For example, negativeacid-hardening photoresists typically require post-exposure heating toinduce the acid-promoted crosslinking reaction, and many chemicallyamplified positive-acting resists require post-exposure heating toinduce an acid-promoted deprotection reaction. Typically post-exposurebake conditions include temperatures of about 50° C. or greater, morespecifically a temperature in the range of from about 50° C. to 160° C.

The exposed resist coating layer is then developed, preferably with anaqueous based developer such as an inorganic alkali exemplified bytetrabutyl ammonium hydroxide, sodium hydroxide, potassium hydroxide,sodium carbonate, sodium bicarbonate, sodium silicate, sodiummetasilicate, aqueous ammonia or the like. Alternatively, organicdevelopers can be used. In general, development is in accordance withart recognized procedures. Following development, a final bake of anacid-hardening photoresist is often employed at temperatures of fromabout 100 to 150° C. for several minutes to further cure the developedexposed coating layer areas.

The developed substrate may then be selectively processed on thosesubstrates areas bared of photoresist, for example chemically etching orplating substrate areas bared of photoresist in accordance withprocedures well known in the art. Suitable etchants include ahydrofluoric acid etching solution and a plasma gas etch such as anoxygen plasma etch. A plasma gas etch removes the crosslinkedantihalation coating layer.

All documents mentioned herein are incorporated herein by reference. Thefollowing non-limiting examples are illustrative of the invention.

EXAMPLE 1 Preparation of Preferred Antireflective Composition ResinBinders

Hydroxyethyl methacrylate (HEMA)/methylanthracene methacrylate (ANTMA)copolymer (Formula I above) was prepared as follows.

A 300 ml 3N round bottom flask equipped with magnetic stirrer,condenser, nitrogen and vacuum inlet was charged with 16.0 g (0.1229mol) HEMA (purified by distillation), 8.49 g (0.0307 mol)methylanthracene methacrylate, 0.2449 g (1 wt. %) AIBN and 180 ml THF.The reaction flask was quenched in liquid nitrogen while being purgedwith nitrogen. When the contents of the reaction flask were frozen, theflask was evacuated, then purged with nitrogen (3 times). The reactionmixture was stirred under reflux for 18 hours. The pale yellow polymerwas precipitated into 3000 ml ether, filtered, then dried at 50° C.under vacuum (yield 86%) to provide the HEMA/ANTMA copolymer having 81mole percent of --CH₂ C(CH₃)(CO₂ CH₂ CH₂ OH)-- units and 19 mole percentof --CH₂ C(CH₃)(CO₂ CH₂ -9-anthracene) units, a Mn of 2295, Mw of 19150and a Tg of 101° C.

EXAMPLE 2 Preparation of di(4-t-butylphenyl)iodonium(+/-)-10-camphorsulfonate

The PAG 1 above can be prepared as follows. A 2 L 3 neck round bottomflask was charged with potassium iodate (214.00 g, 1.00 mol),t-butylbenzene (268.44 g, 2.00 mol) and acetic anhydride (408.36 g, 4.00mol). The flask was fitted with an efficient overhead paddle stirrer, athermometer and a pressure equalizing dropping funnel fitted with a N₂bubbler. The reaction mixture was cooled to 10° C. in a ice-water bathand concentrated sulfuric acid (215.78 g, 2.20 mol) added dropwise viathe addition funnel. The addition was carried out at such a rate as tomaintain the reaction temperature around 25° C. and required 2 hours. Asthe addition proceeded the starting white suspension becameorange-yellow in color. Once the addition was over, the reaction mixturewas stirred at room temperature (20° C.) for an additional 22 hours. Thereaction mixture was cooled to 5-10° C. and water (600 ml) was addeddropwise over a period of 30 minutes, maintaining the temperature below30° C. (Note the first @75 ml should be added at a particular slow rateas to control the initial exotherm, thereafter the rest of the water maybe added at a faster rate). This cloudy mixture was washed with hexane(3×100 ml) (to remove unreacted t-butylbenzene and some4-t-butyliodobenzene byproduct) in a 2 L separating funnel and theaqueous solution of diaryliodonium hydrogensulfate transferred to a 3 Lreaction vessel. The solution was cooled to 5-10° C.,(+/-)-10-camphorsulfonic acid (232.30 g, 1.00 mol) was added in oneportion with stirring and the solution was then neutralized withammonium hydroxide (620 ml, 9.20 mol). The amount of base used was thetheoretical amount required to neutralize all acidic species in the pot,assuming quantitative reaction. The addition of the base is carried outat such a rate as to keep the temperature below 25° C. and takes about 1hour. As the addition nears completion and the pH of the reactionmixture approaches 7, the crude diaryliodonium camphorsulfonateprecipitated as a tan solid. This suspension was allowed to stir at roomtemperature for 3 hours and the material isolated as follows: The tansolid was collected by suction filtration and while still moist taken upin dichloromethane (1 L) and washed with dilute ammonium hydroxide (2.5wt %, 5 ml 14.8 N NH₄ OH+195 ml H₂ O) until the washings are in the pH7-8 range (1×200 ml) and then water (2×200 ml) to restore the pH toaround 7. After drying (MgSO₄), the dichloromethane was removed underreduced pressure and the residue further dried in vacuo at 50° C. for 16hours to give the crude product as a tan solid (390.56 g). The resultingtan solid was then purified by recrystallization in the followingmanner. The tan solid was dissolved in the minimum amount of refluxingisopropanol (@ 375 g PAG in @ 1150 ml IPA) in a 2 L round bottom flaskto give a homogeneous dark red solution. The hot solution wastransferred to a 2 L conical flask and allowed to cool. While thissolution was still warm, hexane (500 ml) was added and crystals formedsoon after. The crystallizing mixture was allowed to cool to roomtemperature and stored for 4 hours. The crystallizing solution wascooled to @ 5° C. in an ice-water bath for 1.5 hours and then the solidwas collected by suction filtration and washed until white with verycold isopropanol-hexane (1:3, 2×200 ml, prepared by cooling the solventmixture in a dry ice-acetone bath before use). The white solid was driedunder aspirator vacuum for 1 hour until the PAG(di-(4-t-butylphenyl)iodonium (+/-)-10-camphor sulfonate) was isolatedas a free flowing white powder. At this stage about 285 g of PAG isobtained. A second recrystallization can be performed in a similarmanner.

Examples 3-4 and Comparative Examples 1A-B and 2

Preparation and Use of Antireflective Compositions of the Invention andComparative Examples

EXAMPLE 3

A preferred antireflective composition of the invention was prepared bymixing the components set forth below, with component amounts expressedas parts by weight based on total weight of the liquid antireflectivecoating composition:

1) Resin binder: 2.17% Polymer (novolac resin base with approximately 4%glycidyl groups replacing OH, and approximately 80% of OH groupsreplaced by --O(C═O)CH₂ 9-anthracene)

2) Crosslinker: 0.61% Powderlink 1174 (American Cyanamid)

3) Acid: 0.06% p-toluene sulfonic acid

4) Photoacid generator: 0.16% di-t-butyl diphenyl iodoniumcamphorsulfonate

5) Surfactant: 0.03% FC 171 (3M Co.)

6) Solvent: 18% ethyl lactate; 10% cyclohexanone; and 68.97% propyleneglycol monomethyl ether

The antireflective composition was spin coated onto a single crystalsilicon substrate 100 mm in diameter, and baked on a vacuum hot plate at175° C. for 60 seconds. The resulting thickness was 600 angstroms. Overthis antireflective composition layer a commercially available DUVpositive photoresist (sold under the tradename of UVIIHS and availablefrom the Shipley Company) was applied to a thickness of 7950 Å after avacuum hot plate bake at 135° C. for 60 seconds. The overcoated resistlayer was exposed to KrF excimer radiation (248 nm) with an ISI XLSprojection stepper through a mask patterned with small lines and spaceswith a dose of 12.0 mJ/cm². The wafer was then baked on a vacuum hotplate at 130° C. for 90 seconds, and then developed with CD-26 developer(Shipley Co.; alkaline aqueous solution) for 60 seconds. Resist footingwas measured by cross-section SEMs (scanning electron micrographs) forboth isolated and dense lines 0.25 μm wide and averaged 3 nm.

COMPARATIVE EXAMPLE 1A

The same antireflective composition was prepared as described above inExample 3, except the photoacid generator was omitted. Thisantireflective composition was spin coated onto a single crystal siliconsubstrate 100 mm in diameter, and baked on a vacuum hot plate at 205° C.for 60 seconds. The resulting thickness was 600 angstroms. Over thisantireflective composition layer a commercially available DUV positivephotoresist (sold under the tradename of UVIIHS and available from theShipley Company) was applied to a thickness of 7950 Å after a vacuum hotplate bake at 135° C. for 60 seconds. The overcoated resist layer wasexposed to KrF excimer radiation (248 nm) with an ISI XLS projectionstepper through a mask patterned with small lines and spaces with a doseof 10.5 mJ/cm². The wafer was then baked on a vacuum hot plate at 130°C. for 60 seconds, and then developed with CD-26 developer (Shipley Co.;alkaline aqueous solution) for 60 seconds. Resist footing was measuredby cross-section SEMs for both isolated and dense lines 0.25 μm wide andaveraged 39 nm.

COMPARATIVE EXAMPLE 1B

The same antireflective composition was prepared as described above inExample 3, exceptN-(perfluoro-1-octanesulfonyloxy)-5-norbornene-2,3-dicarboximide wassubstituted for the diphenyl iodonium camphorsulfonate PAG of Example 3.N-(perfluoro-1-octanesulfonyloxy)-5-norbornene-2,3-dicarboximide is lessthermally stable than diphenyl iodonium camphorsulfonate and can undergodecomposition at about 150° C. This antireflective composition was spincoated onto a single crystal silicon substrate 100 mm in diameter, andbaked on a vacuum hot plate at 175° C. for 60 seconds. The resultingthickness was 600 angstroms. Over this antireflective composition layera commercially available DUV positive photoresist (sold under thetradename of UVIIHS and available from the Shipley Company) was appliedto a thickness of 7950 Å after a vacuum hot plate bake at 130° C. for 60seconds. The overcoated resist layer was exposed to KrF excimerradiation (248 nm) with an ISI XLS projection stepper through a maskpatterned with small lines and spaces with a dose of 12.0 mJ/cm². Thewafer was then baked on a vacuum hot plate at 135° C. for 90 seconds,and then developed with CD-26 developer (Shipley Co.; alkaline aqueoussolution) for 60 seconds. Resist footing was measured by cross-sectionSEMs for both isolated and dense lines 0.25 μm wide and averaged 17 nm.

EXAMPLE 4

A further preferred antireflective composition of the invention wasprepared by mixing the components set forth below, with componentamounts expressed as parts by weight based on total weight of the liquidantireflective coating composition:

1) Resin binder: 2.48% copolymer of 9-anthrylmethylmethacrylate (26mol%)and 2-hydroxyethylmethacrylate (74 mol%)

2) Crosslinker: 0.36% Powderlink 1174 (American Cyanamid)

3) Acid: 0.04% p-nitrobenzyl tosylate

4) Photoacid generator: 0.04% di-t-butyl diphenyl iodoniumcamphorsulfonate

5) Surfactant: 0.03% FC 431 (3M Co.)

6) Solvent: 97.05% propylene glycol monomethyl ether

The antireflective composition was spin coated onto a single crystalsilicon substrate 100 mm in diameter, and baked on a vacuum hot plate at175° C. for 60 seconds. The resulting thickness was 605 angstroms. Overthis antireflective composition layer a commercially available DUVpositive photoresist (sold under the tradename of UVIIHS and availablefrom the Shipley Company) was applied to a thickness of 8620 Å after avacuum hot plate bake at 135° C. for 60 seconds. The overcoated resistlayer was exposed to KrF excimer radiation (248 nm) with an ISI XLSprojection stepper through a mask patterned with small lines and spaceswith a dose of 11.0 mJ/cm². The wafer was then baked on a vacuum hotplate at 130° C. for 90 seconds, and then developed with CD-26 developer(Shipley Co.; alkaline aqueous solution) for 60 seconds. Resist footingwas measured by cross-section SEMs for both isolated and dense lines0.25 μm wide and averaged approximately 12 nm.

COMPARATIVE EXAMPLE 2

The same formulation was prepared as described above in Example 4,except the photoacid generator was omitted. This formulation was spincoated onto a single crystal silicon substrate 100 mm in diameter, andbaked on a vacuum hot plate at 175° C. for 60 seconds. The resultingthickness was 600 angstroms. Over this antireflective composition layera commercially available DUV positive photoresist (sold under thetradename of UVIIHS and available from the Shipley Company) was appliedto a thickness of 7950 Å after a vacuum hot plate bake at 135° C. for 60seconds. The overcoated resist layer was exposed to KrF excimerradiation (248 nm) with an ISI XLS projection stepper through a maskpatterned with small lines and spaces with a dose of 10.8 mJ/cm². Thewafer was then baked on a vacuum hot plate at 130° C. for 60 seconds,and then developed with CD-26 developer (Shipley Co.; alkaline aqueoussolution) for 60 seconds. Resist footing was measured by cross-sectionSEMs for both isolated and dense lines 0.25 μm wide and averaged 27 nm.

The foregoing description of the invention is merely illustrativethereof, and it is understood that variations and modifications can beeffected without departing from the scope or spirit of the invention asset forth in the following claims.

What is claimed is:
 1. A coated substrate comprising:a substrate havingthereon1) a coating layer of an antireflective composition thatcomprises a) a resin binder, b) an acid or thermal acid generator, andc) a photoacid generator compound; and 2) a coating layer of aphotoresist over the antireflective composition coating layer, thephotoresist comprising a resin and a photoacid generator compound. 2.The coated substrate of claim 1 wherein the photoresist is achemically-amplified positive-acting photoresist that comprises a resinbinder and a photoacid generator compound.
 3. The coated substrate ofclaim 1 wherein the antireflective composition photoacid generatorcompound and the photoresist photoacid generator compound each generatesubstantially the same acid compound upon exposure to activatingradiation.
 4. The coated substrate of claim 1 wherein the antireflectivecomposition photoacid generator compound and the photoresist photoacidgenerator compound each generate the same acid compound upon exposure toactivating radiation.
 5. The coated substrate of claim 4 wherein theantireflective composition photoacid generator compound and thephotoresist photoacid generator compound each generate a sulfonate acidupon exposure to activating radiation.
 6. The coated substrate of claim1 wherein the substrate is a microelectronic wafer, a flat panel displaysubstrate or an optical-electronic substrate.
 7. The coated substrate ofclaim 1 wherein the photoacid generator of the antireflectivecomposition is substantially stable upon exposure to temperatures offrom about 110 to 175° C. for at least about 1 minute.
 8. The coatedsubstrate of claim 1 wherein the photoacid generator of theantireflective composition generates acid upon exposure to an effectiveamount of radiation having a wavelength of about 248 nm or 193 nm. 9.The coated substrate of claim 1 wherein the photoacid generator of theantireflective composition has one or more substitited or unsubstitutedalkyl or substituted or unsubstituted alicyclic groups having 4 or morecarbons.
 10. The coated substrate of claim 3 wherein the antireflectivecomposition photoacid generator compound and the photoresist photoacidgenerator compound generate upon exposure to activating radiationphotoacid products that differ about 1.5 or less in pka values.
 11. Thecoated substrate of claim 3 wherein the antireflective compositionphotoacid generator compound and the photoresist photoacid generatorcompound generate upon exposure to activating radiation photoacidproducts that differ in molecular weight by about 20 percent or less.12. The coated substrate of claim 4 wherein the antireflectivecomposition photoacid generator compound and the photoresist photoacidgenerator compound each generated a halo-acid upon each to activatingradiation.
 13. The coated substrate of claim 1 wherein theantireflective composition resin binder comprises anthracenyl units. 14.The coated substrate of claim 1 wherein the antireflective compositionresin binder comprises quinolinyl, hydroxyquinolinyl, phenanthrenyl oracridine groups.
 15. The coated substrate of claim 1 wherien theantireflective composition comprises a crosslinker.
 16. The coatedsubstrate of claim 15 wherein the crosslinker is an amine-basedmaterial.
 17. The coated substrate of claim 16 wherein the crosslinkeris a glycouril resin.
 18. A coated substrate comprising:a substratehaving thereon1) a coating layer of an antireflective compositioncomprising a resin binder, and a photoacid generator, the antireflectivecomposition at least essentially free of a crosslinker component; and 2)a coating layer of a chemically-amplified positive-acting photoresistover the antireflective composition coating layer, the photoresistcomprising a resin and a photoacid generator compound.
 19. The coatedsubstrate of claim 18 wherein the photoacid generator of theantireflective composition is substantially stable upon exposure totemperatures of from about 110 to 175° C. for at least about 1 minute.20. The coated substrate of claim 18 wherein the photoacid generator ofthe antireflective composition generates acid upon exposure to aneffective amount of radiation having a wavelength of about 248 nm or 193nm.
 21. The coated substrate of claim 18 wherein the photoacid generatorof the antireflective composition has one or more substitited orunsubstituted alkyl or alicyclic groups having 4 or more carbons. 22.The coated substrate of claim 18 wherein the antireflective compositionphotoacid generator compound and the photoresist photoacid generatorcompound generate upon exposure to activating radiation photoacidproducts that differ about 1.5 or less in pka values.
 23. The coatedsubstrate of claim 18 wherein the antireflective composition photoacidgenerator compound and the photoresist photoacid generator compoundgenerate upon exposure to activating radiation photoacid products thatdiffer in molecular weight by about 20 percent or less.
 24. The coatedsubstrate of claim 18 wherein the antireflective composition photoacidgenerator compound and the photoresist photoacid generator compound eachgenerate substantially the same acid compound upon exposure toactivating radiation.
 25. The coated substrate of claim 18 wherein theantireflective composition photoacid generator compound and thephotoresist photoacid generator compound each generate the same acidcompound upon exposure to activating radiation.
 26. The coated substrateof claim 18 wherein the antireflective composition photoacid generatorcompound and the photoresist photoacid generator compound each generatea halo-acid upon exposure to activating radiation.
 27. The coatedsubstrate of claim 18 wherein the antireflective composition photoacidgenerator compound and the photoresist photoacid generator compound eachgenerate a sulfonate acid upon exposure to activating radiation.
 28. Thecoated substrate of claim 18 wherein the antireflective compositionresin binder comprises anthracenyl units.
 29. The coated substrate ofclaim 18 wherein the antireflective composition resin binder comprisesquinolinyl, hydroxyquinolinyl, phenanthrenyl or acridine groups.